Preparation of metal-organic compounds



get. 30, 1953 of CICId reocfed p H. M. OLSON 2,573,049

PREPARATION OF METAL-ORGANIC COMPOUNDS Filed Aug. 31, 1950 m Wafer andcacencocld 20 l l I I I00 200 300 400 Mmures Reocnor Tlme & Wczrer cindocehc CLCId i 80- fi 3 Acenc OICIOI L G 0 40 N I J 300 400 20 HMQIsonINVENTOR- [00 200 4 Mmures Reacrlon Time /7%/ awv FI g. 2

AHy.

' nesium, and calcium.

Patented Oct. 30, 1951 PREPARATION OF METAL-ORGANIC COMPOUNDS Harold M.Olson, Vex-million, Ohio, assignor to The Harshaw ChemicalCompanmElyria, Ohio,

a corporation'of Ohio:

April-cast ngs '1, 1950, Serial No. 182,599

This invention relates to manufacture of metal-organic compounds bydirect reaction between a carboxylic acid and the ,metal in the metallicstate. r V

. This application is a continuation in-partof my co-pending applicationSerial No.765,6.37 filed 5 August 1, 1947, now abandoned.

Prior to my invention it was known that such reactions would occursimplyby bringing together the acid and the metal, but the reactionsdidnot go to completion and the rate w as too slow for practicalresults. The ordinary means for increasing reaction rates did notaccelerate these reactions to a sufficient degree. U. S. Patents2,395,397 and 2,397,767 disclose processes by means of which it isproposed to solve the problem by blowing the reaction with air,presumably .to form oxide at the surface of the metal which would easilyreact with the acid. This was found to be unsuitable for the productionof siccatives m and allied products inasmuch as the product was dark andsludged badly, evidently due to the formation of oxidation products".

I have now discovered that certain metals in the metallic state can bereacted with-organic acids at a satisfactory ratey'and to asatisfactorydegree of completion, by carrying out the reaction in the presence-ofwater, or water plus lower aliphatic acids.

In the accompanying drawings, Fig. 1 a graphic representation of thereaction rates in the cases of 2-ethyl hexoic acid employing as:cata'-lyst: water, a mixture of water and acetic acid, and acetic acid alone;and Fig. 2 is a similar graph representing reaction rates in thecase ofnaphthenic acid, the metal being manganese in-both cases.

The metals referred to are manganese, mag- The organic acids referred toare aliphatic and alicyclic organic acids having from 8 t0'22- carbonatoms in the molecule. The monocarboxylic acids are preferred. Thespecific commercial materials which we consider most suitable for ourprocess are naphthenic acid and the higher fatty acids having from 8 to22 carbon atoms in the molecule such as stearic acid, palmitic acid,oleic acid, and Z-ethyl hexoic acid. The list may also include tall oil,tall oil acids, rosin, rosin acids, and other commerical mixtures ofacids such as those derived from fish oil, corn oil, cocoanutoil,linseed oil, castor oil, and cottonseed oil. These mixtures are made upentirely, or almost entirely, of acids having from 8 to 22 carbonatoms."

The lower aliphatic acids referred] to are formic, acetic, chloracetic,propionic, *chloropropionic, oxalic, citric, and tartaric acids.

In the practice of the invention the metal in the form of powder,granules, wire, shavings or the like is brought into contact with (1)the high 50 molecular: weight organic acid,.or a mixture of such highmolecular weight acids, andv (2) a small proportion of water, or the lowmolecular weight acid or, preferably, amixture of water andthe lowmolecular weight acid. The weights of the metal-and the high molecularweight acid may be calculated to stoichiometric proportions, or theremay be an excess of the metal or a small excess of the acid. The lowmolecular weight acid is most desirably employed in relatively lowproportions, e. g. from to 5% based upon the weight of the highmolecular weight acid. Water is most desirably presentto the extent offrom 1 ,1 7,, to 5% of the weight of the high molecular weight acid and,if both catalytic acid and water are used, they may be present, takentogether, to the extent of from to 10% of the weight 01' the highmolecular weight acid. These are merely optimum proportions and largerpropor tior rs may be used. It is not desirable to use more than 10% ofcatalyst since greater proportions reduce reactivity, and increase theproblem j o' I' removal of catalystfromthe product. gases are not onlyunnecessary 'but are actually. objectionable. Inert or reducing gasesmay be employed either by bubbling the same through the reactionmixture, or using such gases to replace the air in the reaction vessel.

The metal may be in excess of the molecular equivalent of the highmolecular weight acid by any amoimt since the excess at the end of thereaction may be filtered off. a; finely divided state which gives fasterreaction and is, therefore, desirable, the excess need not be great; butin order to get a high reaction rate in the case where the metal is notfinely divided, a greater excess is used. In the case of 200 mesh metalan excess of A, mol of metal per mol of high molecular weight acid issatisfactory from the standpoint of reaction rate.

The temperature of the reaction may be suitably from Crto 160 C. butpreferably Should be from C. to CL In some cases the reaction carriedout in the The following specific examples will serve to illustrate theinvention:

Example I To 200 grams of 2-ethyl hexoic acid were added 38.5 grams ofmanganese metal in the form of I00 mesh powder, 5 grams of distilledwater, and 325 grains -of mineral spirits. The mixture was,

refluxed at a temperature of approximately, 130? If the metal is in (I.to 13 5? g fortheperiods of time as indicated in the foiiowingtalfil'e'z. I V

,The/ resulting mixture was refluxed at tempera-= 1mm; 3 2 ".1% .f.1C-.Lq' h t and with the results as indicated in the following Reaction 1table 2 Acld Per Cent-=- Sample z Num her Reaction l .1. ..V.,.-.,, a.7.. Reaction Acid Per Cent Sam 1e Tune 0 +1436 0 p (Minutes) NumberReactlon .043 ail-3 .111. .f 1131 v .72 +123 .91 I, "-'-105" '*-'F2.'-9"18:0 0 +1420 0 165 +0. 5 99. 6 82 +26. 1 81. 6 291 0. 3 100+ 140 +10. 792. 5 ---';'.e,. .w-i 5:; Ear; 5.21.171 1 -7 E l I 2 11 0 97.

m' e I 384 -0.7 100+ To 200 grams of Z-ethyl hexoic acid were added 4465 38.5 grams of .manganesemetalim .the .:form*- of 10.0. .mesh;powder,.:2;5. grams not distilledrwater,

rsamplc (Minutes) Number Reaction or g 6101303010 tacid and aze n s ofmineral 'b i i iw fi e ed ll a. mpera.- tiir 'of'afibroiiimatly I" c. to135 for-the umes anu with'thersiilts' as"indicatdfintheifollofwingtabl'e': I w

eat: 10D

, I Acid .Rer Gent sample i gig Number Reaction 21 1 .9, 1-1402. 21- 2.L 44 +76. 6 4 8. 6 2173, -72 +60; 7 -59. 4 21- +5 05.5 21-- 160 2P37. 175. 2 21 5 .280 .-|-.19.'3 a 8702 21-7. 354 +10. 5 V 93.0 21-8. 402 +9f493. 8

acid value 2 38.3 were added 24 gramsofmanganese metal in theform of710.0 mesh. powder, 2.5 grams of distilled water, 2 5 gramsof.glacialacetic a'c'i'd, ans-1, gram s of;.mineral spirits. The re..-sulting inixture was refluxed at a temperature irom 134 C. to 145 C. iprtljle periods and with Eramiale v I r To 200 gram-S161'refiaiinabhtfieni 56105051010 value 235.3 were aaqe24g msb1 ""hs'e metarmt ermof IOOnie ider, msuueawanen 'hd' raterams tifuiineralsfiiritsl ReactionAcld Per Cent Sample Number 110505611 21 1 0 +1527 .0. 21=2 s3 q-esss"58:2 2 -3 144 +310 115,4 21-4 201 +33. 9 711 8 21:5 250 +204 7 21-6 322+25. 4 J 83. 4 21-7 380 +21. 1 86.2 2r-s 443' +190 81:0

swamp-ze- VI I 'I o, 200grams'of talloiliwere addedi20 grams, ofmanganese intheformof mesh powder, 2. /2 gramspf acetic acid,,2 gramsofwater, and 200, grams. of, mineral spirits. The mixture wasrefluxedipn ,hours at from 135. .C. to 140 C.. The resulting manganesetall oil .soap solution, after distilling off the water, v contained59.1% solids ,atv10.5 .C..,; analyzed 4.82%. of manganese, and had anacid value of minus 11.8. v 1

Example VIII eI QL QO sramspi .i ia h h iiie ac f a valu er eddedlfllaai v ma siu b in s. 5 grams of Water, 5 grams of glacial acetic acid,M425 sramsmi p irit The x ure refluxed for 6 hours at from 135 C. to 110 C. aftenwhiq a he t rwa oved byvacuum distillation. The product, asolution of mag.- e i m .na h h nat con n 2 ha anlacid .value,ofv plus16.4, and contained 62.9% solids at C.

"ExamijZe-IX To 200 gramsof linseed fatty acids were added em 9i alq m mt in the fo m t n.- in /2sr. s o glacia et acid, Zks ms (if. wate 65rams mineral ri 1 129 grams el csq vei t R999 is sity The x rewa ifefluged forfi hours at from C. to C. The water was then distilled 011 undervacuum, and tihelfinal product a solution of calcium linoleate inmineral spirits, v was filtered. It analyzed "2.8 7 of calciumand theacid value was plus 19.4. .It contained 56.9% solids at 105 C.

"Example X I T0200 gfrjamsbr gum rosin were added z'cgrain's otmaiiafisc'inetal'inthe form of 100inesh powder, 5 grams water, 5 grams aceticacid, and 500 grams toluol. The mixture was refluxed for 6 hours at112-l15 C. after which it was filtered and the moisture and toluol werestripped off under vacuum. A solid material containing 8.75% Mn. wasobtained.

Having thus described my invention, what I claim is:

1. In the manufacture of compounds of metals of the class consisting ofmanganese, magnesium, and calcium, the steps of reacting together in thetemperature range from 100 C. to 160 0., metal in the metallic state anda high molecular weight, organic monocarboxylic acid of the classconsisting of aliphatic, alicyclic, rosin, and tall oil acids havingfrom 8 to 22 carbon atoms in the molecule, the metal being present inexcess of the amount required to react with said acid, and the reactionbeing carried out in the presence of a catalyst of the class consistingof water, and a mixture of water with a low molecular weight organicacid of the class consisting of formic,

acetic, propionic, oxalic, citric, and tartaric acids.

2. In the manufacture of compounds of metals of the class consisting ofmanganese, magnesium. and calcium, the steps of reacting together in thetemperature range from C. to 0., metal in the metallic state and a highmolecular weight, organic monocarboxylic acid of the class consisting ofaliphatic, alicyclic, rosin, and tall oil acids having from 8 to 22carbon atoms in the molecule, the metal being present in excess of theamount required to react with said acid, and the reaction being carriedout in the presence of a catalyst of the class consisting of water, anda mixture of water with a low molecular weight organic acid of the classconsisting of formic, acetic, propionic, oxalic, citric, and tartaricacids, each of said catalysts being employed in quantity within therange from to 5% based on the weight of said high molecular weightorganic acid.

3. A process according to claim 2 wherein said metal is manganese, andsaid monocarboxylic acid is naphthenic acid.

4. A process according to claim 2 wherein said metal is manganese, andsaid monocarboxylic acid is 2-ethyl hexoic acid.

5. A process according to claim 2 wherein said metal is magnesium, andsaid monocarboxylic acid is naphthenic acid.

6. A process according to claim 2 wherein said metal is manganese, andsaid monocarboxylic acid is tall oil acid.

7 A process according to claim 2 wherein said metal is calcium, and saidmonocarboxylic acid is naphthenic acid.

HAROLD M. OLSON.

No references cited.

1. IN THE MANFACTURE OF COMPOUNDS OF METALS OF THE CLASS CONSISTING OFMANGANESE, MAGNESIUM, AND CALCIUM, THE STEPS OF REACTING TOGETHER IN THETEMPERATURE RANGE FROM 100* C. TO 160* C., METAL IN THE METALLIC STATEAND A HIGH MOLECULAR WEIGHT, ORGANIC MONOCARBOXYLIC ACID OF THE CLASSCONSISTING OF ALIPHATIC, ALICYCLIC, ROSIN, AND TALL OIL ACIDS HAVINGFROM 8 TO 22 CARBON ATOMS IN THE MOLECULE, THE METAL BEING PRESENT INEXCESS OF THE AMOUNT REQUIRED TO REACT WITH SAID ACID, AND THE REACTIONBEING CARRIED OUT IN THE PRESENCE OF A CATALYST OF THE CLASS CONSISTINGOF WATER, AND A MIXTURE OF WATER WITH A LOW MOLECULAR WEIGHT ORGANICACID OF THE CLASS CONSISTING OF FORMIC, ACETIC, PROPIONIC, OXALIC,CITRIC, AND TARTARIC ACIDS.